JPWO2014208757A1 - Anti-aging agent, rubber composition, and tire - Google Patents

Abstract

A rubber composition comprising an anti-aging agent synthesized from a biological resource including a plant resource and having a value of δ13C of the anti-aging agent of −30 ‰ to −26.0 ‰, or −22 ‰ or more, and Provided is a tire using the rubber composition.

Description

  The present invention relates to an anti-aging agent that does not use fossil resources as a starting material, a rubber composition containing the anti-aging agent, and a tire using the rubber composition.

In recent years, methods for refining fuel oil from bio-derived renewable resources (so-called biomass) including plant resources have been proposed due to increasing demands for reducing fossil resource consumption and greenhouse gas emissions. (See Patent Document 1). Such a fuel oil is called a biofuel, and since it does not increase the total amount of carbon dioxide emission, it is expected in the future as a substitute for a fuel oil derived from fossil resources.
Many compounds derived from fossil resources have been used not only in the field of fuel oil, but also in fields such as household appliances, household goods, and automobiles, but in the same way as fuel oil, in order to reduce dependence on fossil resources, There is a need for a method of making compounds from biomass as an alternative to compounds whose resources are starting materials. As an example, also in the field of automobiles, a method for producing a compound as a tire material from biomass is required.

JP 2009-046661 A

  An object of the present invention is to provide an anti-aging agent synthesized from biological resources including plant resources, a rubber composition containing the anti-aging agent, and a tire using the rubber composition.

The present invention
[1] An anti-aging agent synthesized using biological resources including plant resources,
An anti-aging agent having a value of δ13C of the anti-aging agent of −30 ‰ to −26.0 ‰, or −22 ‰ or more,
[2] The anti-aging agent according to [1], wherein the value of δ13C is −28.5 ‰ to −26.5 ‰.
[3] An anti-aging agent synthesized using biological resources including plant resources, wherein the anti-aging agent has a Δ14C value of −75 ‰ to −225 ‰,
[4] An anti-aging agent synthesized using biological resources including plant resources, wherein the anti-aging agent has a ¹⁴ C decay per gram amount value of 0.1 dpm / g C or more. Agent,
[5] The anti-aging agent according to any one of [1] to [4], wherein the anti-aging agent is synthesized using biomethane obtained from biological resources including plant resources as a starting material,
[6] The anti-aging agent according to any one of [1] to [5], wherein the anti-aging agent is synthesized using biobenzene obtained from biological resources including plant resources as a starting material,
[7] The anti-aging agent is at least one selected from N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,3-dihydroquinoline polymer. The anti-aging agent according to any one of [1] to [6],
[8] The antiaging agent according to any one of [1] to [7], wherein the antiaging agent is synthesized using acetone obtained from a biological resource including a plant resource.
[9] The antiaging agent according to any one of [1] to [8], wherein the antiaging agent is synthesized using methyl isobutyl ketone obtained from a biological resource including a plant resource.
[10] A rubber composition comprising the antiaging agent according to any one of [1] to [9],
[11] A tire including the rubber composition according to [10] is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-aging agent synthesize | combined from the biological origin resources containing a plant resource, the rubber composition which mix | blended this anti-aging agent, and the tire using this rubber composition can be provided.

It is explanatory drawing explaining the method of synthesize | combining an anti-aging agent from the biological origin resources containing a plant resource.

Hereinafter, the anti-aging agent according to the embodiment of the present invention will be described in detail.
[Anti-aging agent]
The anti-aging agent according to the first embodiment of the present invention is an anti-aging agent synthesized from biological resources including plant resources, and the value of δ13C of the anti-aging agent is −30 ‰ to −26.0 ‰. Or -22 ‰ or more. Here, the value of δ13C of the antiaging agent is measured by a stable isotope ratio measuring device.

δ13C represents the ratio of stable isotopes in the substance. δ13C is the ratio of ¹³ C to ¹² C in the target substance, and ¹³ C / ¹² C is compared to the isotope ratio in the standard sample (fossil of Cretaceous belemnite). This is an index indicating how much the deviation is, and this ratio is represented by ‰ (percentage). It means that the ratio of ¹³ C in a substance is so low that the value (negative value) of (delta) ^13C leaves | separates from zero.
Light isotopes are more diffusive and more reactive than heavy isotopes. For example, in the case of carbon atoms of carbon dioxide in the atmosphere taken into plants by photosynthesis, ¹² C is better than ¹³ C. It has been found that it is easily fixed in plants.
That is, the carbon atoms taken into the plant body have a relatively large amount of ¹² C and a smaller amount of ¹³ C than carbon atoms in the atmosphere. Therefore, the stable isotope ratio (δ13C) of carbon taken into the plant body is lower than the stable isotope ratio of carbon existing in the atmosphere.
This change in isotope ratio is called isotope fractionation and is represented by Δ13C (Δ13C is distinguished from δ13C).
Δ13C = (δ13C in the atmosphere) − (δ13C in the sample)
Therefore, the origin substance of an anti-aging agent can be specified from the value of δ13C of the anti-aging agent.
The value of δ13C of the antioxidant is preferably in the range of −21 ‰ to −12 ‰. The value of δ13C of the antioxidant is more preferably in the range of −28.5 ‰ to −26.5 ‰.

The anti-aging agent according to the second embodiment of the present invention is an anti-aging agent synthesized from biological resources including plant resources, and the value of Δ14C of the anti-aging agent is −75 ‰ to −225 ‰. is there.
In addition, the anti-aging agent according to the third embodiment of the present invention is an anti-aging agent synthesized from biological resources including plant resources, and the ¹⁴ C decay rate per gram amount value of the anti-aging agent. Is 0.1 dpm / gC or more.
Here, the value of Δ14C of the anti-aging agent is a value converted to ¹⁴ C concentration ( ¹⁴ AN) when it is assumed that the sample carbon is δ13C = −25.0 ‰. In addition, the value of δ13C of the antiaging agent was measured by a stable isotope ratio measuring device.
Δ14C can be calculated from the above-described value of δ13C as follows.
δ14C = [( ¹⁴ As− ¹⁴ AR) / ¹⁴ AR] × 1000 (1)
δ13C = [( ¹³ As− ¹³ APDB) / ¹³ APDB] × 1000 (2)
here,
¹⁴ As: ¹⁴ C concentration of sample carbon: ( ¹⁴ C / ¹² C) s or ( ¹⁴ C / ¹³ C) s
¹⁴ AR: ¹⁴ C concentration of standard modern carbon: ( ¹⁴ C / ¹² C) R or ( ¹⁴ C / ¹³ C) R
¹³ As: ¹³ C concentration of sample carbon: ( ¹³ C / ¹² C) s
¹³ APDB: ¹³ C concentration of Cretaceous Belemnite fossils (PDB): ( ¹³ C / ¹² C) PDB
The ¹⁴ C concentration in the equation (1) is converted based on the following equation based on the measured value of δ13C.
^{14 AN = 14 As × (0.975} / (1 + δ13C / 1000)) 2 ( when using a ¹⁴ C / ¹² C as ¹⁴ As)
Or
^{14 AN = 14 As × (0.975} / (1 + δ13C / 1000)) ( when using ¹⁴ C / ¹³ C as ¹⁴ As)
From the above,
Δ14C = [( ¹⁴ AN− ¹⁴ AR) / ¹⁴ AR] × 1000 (‰)

The value of Δ14C of the anti-aging agent is −75 ‰ to −225 ‰, which is the same level as Δ14C of carbon in carbon dioxide in the present air, and it is an organic matter fixed in the existing growing plant body. Means contained carbon.
Since the half-life of radioactive carbon ¹⁴ C is about 5730 years, carbon contained in fossil resources does not include ¹⁴ C. Δ14C of butadiene derived from fossil resources is about −1000 ‰.
Therefore, the origin of the anti-aging agent can be specified by the Δ14C value of the anti-aging agent, the ¹⁴ C decay per gram amount per minute, or the value of δ 13C.

The anti-aging agent synthesized from biological resources including plant resources is hereinafter referred to as bio-derived anti-aging agent.
As the bio-derived anti-aging agent, an amine-based anti-aging agent or a quinoline-based anti-aging agent having a value of δ13C satisfying the above range can be used. In addition, as a bio-derived anti-aging agent, the value of Δ14C satisfies −75 ‰ to −225 ‰, or the amount of ¹⁴ C decay per gram per minute satisfies the value of 0.1 dpm / gC or more. An inhibitor and a quinoline-based anti-aging agent can be used.
Examples of the amine anti-aging agent include N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, alkylated diphenylamine, 4,4. '-(Α, α-dimethylbenzyl) diphenylamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl- p-phenylenediamine, phenyl-α-naphthylamine, octylated diphenylamine and its derivatives, N, N′-diphenyl-p-phenylenediamine, N, N′-diallyl-p-phenylenediamine, N, N′-di-β -Naphtyl-p-phenylenediamine etc. are mentioned.
Examples of the quinoline antioxidant include 2,2,4-trimethyl-1,3-dihydroquinoline polymer, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and 6-dodecyl- Examples include 2,2,4-trimethyl-1,2-dihydroquinoline.
The bio-derived anti-aging agents described above may be used alone or in combination of two or more. Among the bio-derived anti-aging agents described above, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,3-dihydroquinoline polymer are selected. At least one is preferred.
The content of the bio-derived anti-aging agent with respect to the total mass of the anti-aging agent is preferably 10 to 100% by mass.
In addition to the bio-derived anti-aging agent described above, the value of δ13C satisfies the above range, the value of Δ14C satisfies −75 ‰ to −225 ‰, or the decay value per gram per minute of ^14C is Examples thereof include a phenol-based anti-aging agent, an organic phosphite-based anti-aging agent, a thioether-based anti-aging agent and the like that satisfy 0.1 dpm / gC or more.

[Method of synthesizing bio-derived anti-aging agent]
<Synthesis method>
Method for synthesizing bio-derived N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,3-dihydroquinoline polymer as bio-derived anti-aging agents Will be described with reference to FIG.
FIG. 1 is an explanatory diagram for explaining a method of synthesizing an antiaging agent from a biological resource including a plant resource.
The bio-derived anti-aging agent can be synthesized via benzene using methane obtained from biological resources including plant resources (hereinafter referred to as biomethane) as a starting material.

(Biomass → Biomethane: Methane fermentation)
First, biomethane is synthesized from biomass by methane fermentation.
Examples of biological resources that can be used as raw materials for biobenzene include waste biomass such as food waste, food waste, livestock waste, sludge, and vegetation waste. It is known that biogas (methane gas / carbon dioxide = 60/40, including a trace amount of hydrogen sulfide) can be obtained by decomposing these organic substances by microorganisms. By purifying biogas, high-purity methane gas can be obtained.

(Biomethane → Biobenzene: Mo / ZSM-5 catalyst)
Next, biobenzene is synthesized from biomethane. A methane conversion rate of 6-12% was reported in a flow-through fixed bed reactor using a 6% Mo / ZSM-5 catalyst at 750 ° C., 3 atm (Patent No. 3755955, Patent No. 3755968, Patent No. 3745885 and Japanese Patent No. 3835765).

(Production of bio-derived N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,3-dihydroquinoline polymer)
As shown in FIG. 1, N-phenyl-N′-1,3 is obtained by reacting N-phenyl-p-phenylenediamine obtained from aniline produced from bio-derived benzene with methyl isobutyl ketone. -Dimethylbutyl-p-phenylenediamine can be obtained.
In addition, a polymer of 2,2,4-trimethyl-1,3-dihydroquinoline can be obtained by reacting aniline produced from bio-derived benzene with acetone.
Here, a part of the raw material used in the process of synthesizing the bio-derived anti-aging agent may be a fossil resource-derived resource or a biological resource including a plant resource. Further, the raw material may be a mixture of a fossil resource-derived raw material and a biological-derived raw material including a plant resource.
From the viewpoint of the discoloration resistance and crack resistance of the rubber composition and tire using the obtained compound, it is preferable to use a fossil resource-derived resource as a part of the raw material.
For example, the above-mentioned methyl isobutyl ketone and acetone can be bio-derived. Hereinafter, a method for producing bio-derived acetone and a method for producing bio-derived methyl isobutyl ketone will be described.

<Bio-derived acetone>
As an example of a method for producing bio-derived acetone, there are a method of dry distillation of calcium acetate and an acetone / butanol fermentation method.
In the method of dry distillation of calcium acetate, first, calcium acetate is synthesized from acetic acid obtained by thermal decomposition of biomass or oxidative fermentation of ethanol and calcium carbonate. Acetone is obtained by dry distillation (thermal decomposition) of the obtained calcium acetate.
CaCO ₃ + CH ₃ COOH → Ca (OCOCH ₃ ) ₂ + H ₂ O + CO ₂
Ca (OCOCH ₃ ) ₂ → CaCO ₃ + CH ₃ COCH ₃
Specifically, acetone is obtained from calcium acetate according to the methods disclosed in the following documents 1 and 2.
Reference 1: EGR Ardagh, AD Barbour, GE McClelian, EW McBride, Distillation of Acetate of Lime, Ind. Eng. Chem., 1924, 16 (11), pp 1133-1139
Reference 2: LF Goodwin, ET Sterne, Losses Incurred in the Preparation of Acetone by the Distillation of Acetate of Lime, Industrial & Engineering Chemistry, 1920, 12 (3), 240-243
In addition, according to the acetone / butanol fermentation method, acetone is obtained from a saccharide according to the following formula.
95C ₆ H ₁₂ O ₆ → 60C ₄ H ₉ OH + 30CH ₃ COCH ₃ + 10C ₂ H ₄ OH + 220CO ₂ + 120H ₂ + 30H ₂ O

<Bio-derived methyl isobutyl ketone (MIBK)>
Bio-derived methyl isobutyl ketone can be produced through the following steps a to c using the above-described bio-derived acetone as a starting material.
a. Two molecules of acetone are reacted with aldol to obtain diacetone alcohol.
b. Diacetone alcohol is dehydrated and converted to mesityl oxide.
c. When mesityl oxide is hydrogenated, methyl isobutyl ketone is obtained.
Specifically, methyl butyl ketone can be produced according to the method disclosed in Document 3 below.
Reference 3: Organic Syntheses, Coll. Vol. 1, p.199 (1941); Vol. 1, p.45 (1921)

[Rubber composition]
The rubber composition according to the embodiment of the present invention is blended with the bio-derived anti-aging agent of the present invention. The rubber composition further contains other additives such as a rubber component, an inorganic filler, carbon black, and a vulcanization accelerator. A bio-derived anti-aging agent may be used in the rubber composition, and components other than the anti-aging agent can be appropriately selected according to the purpose. Moreover, it is desirable to replace components other than bio-derived anti-aging agents with bio-derived components.

<Rubber component>
There is no restriction | limiting in particular in the rubber component which can be mix | blended with the rubber composition of this invention, According to the objective, it can select suitably.
Examples of the rubber component include butadiene polymer, natural rubber, epoxidized natural rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubber, butyl rubber, bromide of a copolymer of isobutylene and p-methylstyrene, Halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene -Butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber and the like. These may be used individually by 1 type and may use 2 or more types together.

<Rubber component derived from biomass>
The rubber component that can be blended in the rubber composition of the present invention is desirably a rubber component that is synthesized from biological resources including plant resources.
(Bio-butadiene rubber)
An example of a rubber component synthesized from biological resources including plant resources is biobutadiene rubber. Biobutadiene rubber is produced from a biobutadiene monomer obtained by synthesizing bioethanol synthesized from biological resources including plant resources using a starting material.
A bioethanol produced from biomass is brought into contact with a composite metal oxide containing at least magnesium and silicon as metal elements under heating to produce a mixture containing a biobutadiene monomer component. A biobutadiene monomer component is extracted from this mixture, and a butadiene polymer is produced using the extracted biobutadiene monomer component.

  The method for producing the butadiene polymer is not particularly limited, and any of solution polymerization method, gas phase polymerization method, and bulk polymerization method can be used. Among these, the solution polymerization method is preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form. As a polymerization method, any of an anionic polymerization method using an organometallic compound as a polymerization initiator and a coordination polymerization method using a rare earth metal compound as a polymerization initiator can be used.

The butadiene polymer may be a copolymer synthesized from a biobutadiene monomer and a monomer copolymerizable with the biobutadiene monomer. Examples of monomers copolymerizable with the biobutadiene monomer include conjugated diene compounds and aromatic vinyl compounds. Examples of the conjugated diene compound include 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene and the like. In this embodiment, isoprene is excluded from the conjugated diene compound copolymerizable with the biobutadiene monomer.
Examples of the aromatic vinyl compound include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like.
The monomer copolymerizable with the biobutadiene monomer may be either one synthesized from biological resources including plant resources or one derived from petrochemicals. Moreover, the normal butadiene monomer which is not derived from bioethanol may be contained in a predetermined amount.

<Reinforcing filler>
A reinforcing filler can be blended in the rubber composition as necessary. Examples of the reinforcing filler include carbon black and inorganic filler, and at least one selected from carbon black and inorganic filler is preferable.
There is no restriction | limiting in particular in an inorganic filler, According to the objective, it can select suitably. Examples of inorganic fillers include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, and titanium. Examples include potassium acid and barium sulfate. These may be used individually by 1 type and may use 2 or more types together. In addition, when using an inorganic filler, you may use a silane coupling agent suitably.
There is no restriction | limiting in particular in content of a reinforcing filler, According to the objective, it can select suitably. The reinforcing filler is preferably contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the rubber component.
The effect which reinforces a rubber composition as content of a reinforcing filler is 5 mass parts or more is acquired. A rubber component and a reinforcing filler can be mixed as it is 200 mass parts or less, and the performance as a rubber composition can be improved.

<Other additives>
Other additives include anti-aging agents other than bio-derived anti-aging agents. If necessary, vulcanization accelerator, reinforcing agent, softener, filler, vulcanization aid, colorant, flame retardant, lubricant, foaming agent, plasticizer, processing aid, antioxidant, scorch inhibitor, Known materials such as ultraviolet ray inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use. Other additives may also be synthesized from biological resources including plant resources.

[Crosslinked rubber composition]
The rubber composition of the present invention may contain a crosslinking agent in addition to the bio-derived anti-aging agent, rubber component, inorganic filler, carbon black, and other additives of the present invention. A rubber composition containing a cross-linking agent can form a cross-linked cross-linked rubber composition.

<Crosslinking agent>
There is no restriction | limiting in particular in the crosslinking agent which can be used for preparation of a crosslinked rubber composition, According to the objective, it can select suitably. For example, sulfur crosslinking agent, organic peroxide crosslinking agent, inorganic crosslinking agent, polyamine crosslinking agent, resin crosslinking agent, sulfur compound crosslinking agent, oxime-nitrosamine crosslinking agent sulfur and the like can be mentioned. Among these, in the case of a rubber composition for tires, it is preferable to use a sulfur-based crosslinking agent.
There is no restriction | limiting in particular in content of a crosslinking agent, According to the objective, it can select suitably. The crosslinking agent is preferably contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
If content of a crosslinking agent is 0.1 mass part or more, it can bridge | crosslink so that a predetermined effect may be acquired. If it is 20 mass parts or less, it can prevent that a bridge | crosslinking advances during kneading | mixing, and will not impair the physical property of a vulcanizate.

[tire]
The tire of the present invention includes the rubber composition or the crosslinked rubber composition of the present invention. In the tire of the present invention, components other than the rubber composition or the crosslinked rubber composition can be appropriately selected depending on the purpose.
Examples of the application site of the rubber composition or crosslinked rubber composition of the present invention in a tire include treads, base treads, sidewalls, side reinforcing rubbers, and bead fillers. The application site is not limited to these.
The tire of the present invention can be manufactured using a conventional method. For example, on a tire molding drum, members usually used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, the desired tire can be manufactured by heat vulcanizing the green tire according to a conventional method.

[Applications other than tires]
In addition to tire applications, the rubber composition of the present invention for anti-vibration rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, various hoses, Moran, golf balls, shoe soles, anti-skin materials, rubber shoes, etc. The crosslinked rubber composition of the present invention can be used.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
[Evaluation method]
<Measurement of δ13C>
The value of δ13C of the bio-derived anti-aging agent produced from biomethane was measured with a stable isotope ratio measuring device.
<Measurement of Δ14C>
The value of δ13C of the anti-aging agent was measured with a stable isotope ratio measuring device, and Δ14C was calculated by the conversion method described above.
<Measurement of ¹⁴ C decay per gram per minute>
The amount of ¹⁴ C decay per gram of the anti-aging agent was measured by accelerator mass spectrometry (AMS) and liquid scintillation counting method (LSC).

<Evaluation of vulcanization speed>
As for the vulcanization rate, the value of 155 ° C. and Tc (90) was measured by the method specified in JIS K6300-2: 2001. For the measurement, “Charast meter W type” manufactured by Nichigo Corporation was used, and the vulcanized rubber of Comparative Example 1 was represented by 100.
<Evaluation of 300% elongation tensile stress>
The 300% elongation tensile stress was determined in accordance with JIS K 6251. The 300% elongation tensile stress was expressed as an index with the vulcanized rubber of Comparative Example 1 as 100.
<Evaluation of anti-aging effect>
In accordance with JIS K 6259: 2004, the ozone deterioration test of the test piece was performed under the conditions of a temperature of 40 ° C., an ozone concentration of 50 pphm, and an elongation of 20%. After 50 hours, the deterioration state of the test piece was observed and the number of cracks generated evaluated. The vulcanized rubber of Comparative Example 1 was represented by an index of 100. Further, the same ozone deterioration test was performed on the same test piece after one year and further two years later, and the deterioration state was observed. The vulcanized rubber of Comparative Example 1 was represented by an index of 100.

<Discoloration resistance>
The discoloration resistance was evaluated by using a chromaticity meter (manufactured by Nippon Denshoku Industries Co., Ltd., model name “NF333”) to evaluate the discoloration degree of a test piece prepared from a vulcanized rubber composition after vulcanization. The colorimetric data was expressed as L *, a *, b *. The L * value indicates lightness, and the a * value and b * value indicate color. If the a * value and the b * value are 0, the color is colorless. The positive value of the a * value indicates red, and the negative value indicates green. Moreover, yellow is shown as the b * value is positive, and blue is shown as the negative value.
The b * value of the test piece immediately after vulcanization and the color by visual observation, and the test piece after being left under a condition where it is exposed to direct sunlight for a specific time of the day under a roof that is not exposed to rain outdoors in summer. The b * value and the color by visual observation were compared to evaluate the degree of discoloration. The degree of color change is expressed in five levels. That is, 5 is used when the degree of discoloration is severely recognized, 4 when discoloration is observed in more than half of the whole, 3 when discoloration is observed in less than half of the whole, and a case where slight discoloration is observed. 2 and 1 when no discoloration was observed.

[Biobutadiene polymer]
As the butadiene polymer as the rubber component, a biobutadiene polymer obtained by polymerizing a biobutadiene monomer synthesized from a bio-derived renewable resource (biomass) including plant resources was used.
<Manufacture of biobutadiene polymer>
(Manufacture of catalyst)
A silica-magnesia composite oxide synthesized by a sol-gel method was used as a catalyst. The manufacturing method of this catalyst is as follows. First, Mg (OH) ₂ gel was synthesized by dropping 100 mL of a 14% aqueous ammonia solution into a solution of Mg (NO ₃ ) ₂ .6H ₂ O (64 g) dissolved in 100 mL of distilled water. On the other hand, Si (OH) ₄ gel was synthesized by dropping 12.5 mL of 1.38 M nitric acid and 50 mL of 14% aqueous ammonia into a solution of Si (OC ₂ H ₅ ) ₄ (55 mL) dissolved in 150 mL of ethanol. The obtained Mg (OH) ₂ gel was subjected to suction filtration after washing with distilled water, and the Si (OH) ₄ gel was subjected to suction filtration after washing with ethanol. These two kinds of gels were mixed, and the mixed gel was air-dried, then dried at 80 ° C., 500 ° C., and calcined in an N ₂ atmosphere to produce a silica-magnesia composite oxide catalyst.

(Production of biobutadiene monomer)
Bioethanol obtained by fermenting sugarcane, tapioca and corn starches with yeast was used as a starting material.
A biobutadiene monomer was produced by contacting the catalyst produced by the above method with the bioethanol.
As the reaction apparatus, a fixed bed gas flow type catalytic reaction apparatus was used. The manufactured silica-magnesia composite oxide catalyst was filled in a quartz reaction tube, and was subjected to heat treatment at 500 ° C. for 2 hours in a carrier gas atmosphere (N ₂ ; gas flow rate 66 mL / min) as a pretreatment.
After completion of the pretreatment, the temperature of the catalyst tube was lowered to the reaction temperature, and bioethanol gas diluted with N ₂ was introduced. The reaction temperature was 350 ° C. or 450 ° C.
The mixture containing the biobutadiene monomer was recovered by performing the following separation operation on the gas generated by the reaction. First, the product gas was bubbled into hexane, so that the target biobutadiene monomer was dissolved in the solvent. The recovered butadiene solution was purified by drying to further remove impurities such as ethanol, acetaldehyde, diethyl ether, ethoxyethylene, and ethyl acetate.

(Production of biobutadiene polymer)
A nitrogen-substituted 5 L autoclave was charged with a monomer solution in which 2.4 kg of cyclohexane and 300 g of a biobutadiene monomer produced based on the above production example of a biobutadiene monomer were dissolved in a nitrogen atmosphere. To the autoclave, as a catalyst component, a cyclohexane solution of neodymium versatate (0.09 mmol), a toluene solution of methylaluminoxane (MAO, 3.6 mmol), diisobutylaluminum hydride (DIBAH, 5.5 mmol) and diethylaluminum chloride (0. (18 mmol) in toluene and 1,3-butadiene (4.5 mmol) were aged at 40 ° C. for 30 minutes, and a pre-prepared catalyst composition was charged, followed by polymerization at 60 ° C. for 60 minutes. 200 g of this polymer solution was extracted into a methanol solution containing 0.2 g of 2,4-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping and dried with a roll at 110 ° C. To obtain a biobutadiene polymer.

[Manufacture of bio-derived anti-aging agents]
<Production Example 1>
Biomass (methane gas / carbon dioxide = 60/40) was obtained from biomass such as food waste, food waste, livestock waste, sludge, and vegetation waste by decomposing these biomass with microorganisms. Next, the obtained biogas was purified to obtain high-purity methane gas.
Next, biobenzene was synthesized from biomethane using a 6% Mo / ZSM-5 catalyst at 750 ° C. and 3 atm using a flow-through fixed bed reactor. Next, N-phenyl-p-phenylenediamine obtained from aniline produced from bio-derived benzene is reacted with bio-derived methyl isobutyl ketone to thereby prevent N-phenyl-N ′ of anti-aging agent B. -1,3-Dimethylbutyl-p-phenylenediamine was obtained.

<Production Example 2>
In Production Example 1, N-phenyl-N of anti-aging agent C was obtained by the same reaction as in Production Example 1 except that N-phenyl-p-phenylenediamine was reacted with methyl isobutyl ketone derived from a fossil raw material. '-1,3-dimethylbutyl-p-phenylenediamine was obtained.

[Examples 1 and 3 and Comparative Example 1]
A rubber composition was prepared according to the formulation shown in Table 1, and vulcanized at 145 ° C. for 33 minutes to obtain a vulcanized rubber. In Examples 1 and 3, the above-mentioned biobutadiene polymer was used as a rubber component, and in Comparative Example 1, a conventional butadiene rubber was used.
Anti-aging agents B and C are produced by the above production method.
Anti-aging agent A used in Comparative Example 1 is derived from petroleum resources, and is 6PPD “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
For each of the vulcanized rubbers obtained in Examples 1 and 3 and Comparative Example 1, the vulcanization rate, 300% elongation tensile stress, crack resistance, and discoloration resistance were measured and evaluated. The results are shown in Table 2.

* 1: Nitrogen adsorption specific surface area: 42 m ² / g, manufactured by Tokai Carbon Co., Ltd., Seast F
* 2: Microcrystalline wax, manufactured by Nippon Seiwa Co., Ltd., Ozoace 0701
* 3: Vulcanization accelerator DPG: Ouchi Shinsei Chemical Co., Ltd., Noxeller D
* 4: Vulcanization accelerator DM: Ouchi Shinsei Chemical Co., Ltd., Noxeller DM
* 5: Vulcanization accelerator CBS: Sunseller CM-G, manufactured by Sanshin Chemical Industry Co., Ltd.

From Table 2, the value of δ13C of anti-aging agent B blended in Example 1 is −29 ‰, and the value of δ13C of anti-aging agent C blended in Example 3 is −27 ‰. The value of δ13C of the anti-aging agent (type A) formulated in Example 1 was −23 ‰.
From Table 2, the vulcanization speed, 300% elongation tensile stress, crack resistance of the vulcanized rubber obtained by vulcanizing the rubber composition having the biobutadiene rubber of Examples 1 and 3 and the bio-derived anti-aging agent Are the same as those of the vulcanization rate, 300% elongation tensile stress, and crack resistance of the vulcanized rubber obtained by vulcanizing the rubber composition having the petroleum-derived butadiene rubber and the anti-aging agent of Comparative Example 1. Although the value of the grade was shown, it was found that the crack resistance after one year or two years was superior to that of Comparative Example 1 using anti-aging agent A. Further, it was found that the discoloration resistance of the tires produced using the antioxidants of Examples 1 and 3 was superior to that of Comparative Example 1.
The tire manufactured using the bio-derived anti-aging agent has a browning of the tire surface suppressed for a long period of time, that is, has excellent discoloration resistance. This indicates that the bio-derived anti-aging agent has good compatibility with the rubber component.
From this, the vulcanized rubber compounded with the anti-aging agent synthesized from the biological resources including the plant resources is the conventional vulcanization rate, 300% elongation tensile stress, crack resistance and discoloration resistance. It was found to be superior to vulcanized rubber containing an anti-aging agent.
Furthermore, the vulcanized rubber of Example 3 in which a part of the raw materials was blended with an anti-aging agent C using a petroleum-derived material was used as an example of blending an anti-aging agent B in which all the raw materials were derived from bio. It was found that the color change resistance was superior to that of No. 1 vulcanized rubber.

[Examples 2 and 4 and Comparative Example 2]
Examples 2 and 4 and Comparative Example 2 were prepared by preparing a rubber composition according to the formulation shown in Table 3 (using styrene-butadiene copolymer rubber (SBR) as a rubber component) and vulcanizing at 145 ° C. for 33 minutes. A vulcanized rubber was obtained.
In addition, the anti-aging agent mix | blended in Example 2 is synthesize | combined from the biological origin resources containing a plant resource. On the other hand, the antioxidant contained in Comparative Example 2 is derived from petroleum resources. For each vulcanized rubber obtained in Example 2 and Comparative Example 2, the vulcanization rate, 300% elongation tensile stress, crack resistance, and discoloration resistance were measured and evaluated. The results are shown in Table 4.

* 6: JSR, # 1500
* 7: Nitrogen adsorption specific surface area: 93 m ² / g, Tokai Carbon Co., Ltd., Seast KH
* 8: Nippon Sil AQ, manufactured by Tosoh Silica Corporation
* 9: E75, made by Evonik Degussa, Si75
* 10: Vulcanization accelerator DPG: Ouchi Shinsei Chemical Co., Ltd., Noxeller D
* 11: Vulcanization accelerator DM: Ouchi Shinsei Chemical Co., Ltd., Noxeller DM
* 12: Vulcanization accelerator NS: Ouchi Shinsei Chemical Co., Ltd., Noxeller NS

From Table 4, the value of δ13C of anti-aging agent B blended in Example 2 is −29 ‰, and the value of δ13C of anti-aging agent C blended in Example 4 is −27 ‰. The value of δ13C of anti-aging agent A blended in Example 2 was −23 ‰.
From Table 4, the vulcanization rate of the vulcanized rubber obtained by vulcanizing the rubber composition having the petroleum-derived synthetic rubber of Examples 2 and 4 and the bio-derived anti-aging agent, 300% elongation tensile stress The index of crack resistance is the vulcanization rate of a vulcanized rubber obtained by vulcanizing a rubber composition having a synthetic rubber derived from petroleum resources of Comparative Example 2 and a conventional anti-aging agent, 300% elongation tensile stress. Although it showed a value similar to the index of crack resistance, it was found that the crack resistance after one year or two years was superior to that of Comparative Example 2 using anti-aging agent A. Moreover, it was found that the discoloration resistance of the tires produced using the antioxidants of Examples 2 and 4 was superior to that of Comparative Example 2. The tire manufactured using the bio-derived anti-aging agent has a browning of the tire surface suppressed for a long period of time, that is, has excellent discoloration resistance. This indicates that the bio-derived anti-aging agent has good compatibility with the rubber component.
From this, the vulcanized rubber compounded with synthetic rubber and an anti-aging agent synthesized from biological resources including plant resources, vulcanization speed, 300% elongation tensile stress, crack resistance and discoloration resistance, It was found to be superior to the vulcanized rubber compounded with the conventional anti-aging agent.
Furthermore, the vulcanized rubber of Example 4 in which a part of the raw material was blended with an anti-aging agent C using a petroleum-derived material was used as an example of blending an anti-aging agent B in which all the raw materials were derived from bio. It was found to be superior in resistance to discoloration than vulcanized rubber No. 2.

[Examples 5 and 7, Comparative Example 3]
A rubber composition was prepared according to the formulation shown in Table 5, and vulcanized at 145 ° C. for 33 minutes to obtain a vulcanized rubber. In Examples 5 and 7, the above-mentioned biobutadiene polymer was used as a rubber component, and in Comparative Example 3, a conventional butadiene rubber was used.
Anti-aging agents B and C are produced from biological resources including plant resources by the above production method.
Anti-aging agent A used in Comparative Example 1 is derived from petroleum resources, and is 6PPD “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
For each of the vulcanized rubbers obtained in Examples 5 and 7 and Comparative Example 3, the vulcanization rate, 300% elongation tensile stress, crack resistance were measured, and discoloration resistance was evaluated. The results are shown in Table 6.

* 21: Nitrogen adsorption specific surface area: 42 m ² / g, manufactured by Tokai Carbon Co., Ltd., Seast F
* 22: Microcrystalline wax, manufactured by Nippon Seiwa Co., Ltd., Ozoace 0701
* 23: Vulcanization accelerator DPG: Nouchira D, manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 24: Vulcanization accelerator DM: Ouchi Shinsei Chemical Co., Ltd., Noxeller DM
* 25: Vulcanization accelerator CBS: Sunseller CM-G, manufactured by Sanshin Chemical Industry Co., Ltd.

From Table 6, the value of Δ14C of anti-aging agent B formulated in Example 5 is −100 ‰, and the amount of ¹⁴ C decayed per gram per minute is 0.2 dpm / gC. The value of Δ14C of the anti-aging agent C blended in (1) is −200 ‰, the ¹⁴ C decay / gram amount per minute is 0.14 dpm / g C, and the anti-aging agent A blended in Comparative Example 3 is 0.14 dpm / g C. The value of Δ14C was −1000 ‰, and the amount of ¹⁴ C decayed per gram per minute was 0.05 dpm / gC.
From Table 6, the vulcanization speed, 300% elongation tensile stress, crack of the vulcanized rubber obtained by vulcanizing the rubber composition having the biobutadiene rubber and the bio-derived anti-aging agent of Examples 5 and 7 The index of resistance is an index of vulcanization speed, 300% elongation tensile stress, crack resistance of a vulcanized rubber obtained by vulcanizing a rubber composition having a petroleum-derived butadiene rubber and an anti-aging agent of Comparative Example 1. The crack resistance after one year or two years was found to be superior to that of Comparative Example 3 using anti-aging agent A. It was also found that the discoloration resistance of the tires produced using the antioxidants of Examples 5 and 7 was superior to that of Comparative Example 3.
The tire manufactured using the bio-derived anti-aging agent has a browning of the tire surface suppressed for a long period of time, that is, has excellent discoloration resistance. This indicates that the bio-derived anti-aging agent has good compatibility with the rubber component.
From this, vulcanized rubber compounded with antioxidants synthesized from biological resources including plant resources is derived from conventional petroleum resources in terms of vulcanization speed, 300% elongation tensile stress, crack resistance and discoloration resistance. It was found to be superior to the vulcanized rubber compounded with an anti-aging agent.
Furthermore, the vulcanized rubber of Example 7 in which a part of the raw materials was blended with an anti-aging agent C using a petroleum-derived material was used as an example of blending an anti-aging agent B in which all the raw materials were derived from bio. It was found to be superior in discoloration resistance than vulcanized rubber No. 5.

[Examples 6 and 8 and Comparative Example 4]
A rubber composition was prepared according to the formulation shown in Table 7 (using styrene-butadiene copolymer rubber (SBR) as a rubber component), and vulcanized at 145 ° C. for 33 minutes. Examples 6 and 8 and Comparative Example 4 A vulcanized rubber was obtained.
In addition, the anti-aging agent mix | blended in Example 6, 8 was synthesize | combined from the biological origin resources containing a plant resource. On the other hand, the antioxidant contained in Comparative Example 4 is derived from petroleum resources. For each of the vulcanized rubbers obtained in Examples 6 and 8 and Comparative Example 4, the vulcanization rate, 300% elongation tensile stress, crack resistance, and discoloration resistance were measured and evaluated. The results are shown in Table 8.

* 26: JSR, # 1500
* 27: Nitrogen adsorption specific surface area: 93 m ² / g, manufactured by Tokai Carbon Co., Ltd., Seast KH
* 28: Nippon Sil AQ, manufactured by Tosoh Silica Corporation
* 29: E75, made by Evonik Degussa, Si75
* 30: Vulcanization accelerator DPG: Nouchira D, manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 31: Vulcanization accelerator DM: Ouchi Shinsei Chemical Co., Ltd., Noxeller DM
* 32: Vulcanization accelerator NS: Ouchi Shinsei Chemical Co., Ltd., Noxeller NS

From Table 8, the value of Δ14C of anti-aging agent B formulated in Example 6 is −100 ‰, and the amount of ¹⁴ C decayed per gram per minute is 0.2 dpm / gC. The value of Δ14C of the anti-aging agent B blended in (1) is −200 ‰, and the ¹⁴ C decay / gram amount per minute is 0.14 dpm / gC. The value of Δ14C was −1000 ‰, and the amount of ¹⁴ C decayed per gram per minute was 0.05 dpm / gC.
From Table 8, the vulcanization rate of the vulcanized rubber obtained by vulcanizing the rubber composition having the petroleum-derived synthetic rubber of Examples 6 and 8 and the bio-derived anti-aging agent, 300% elongation tensile stress The index of crack resistance is the vulcanization rate of a vulcanized rubber obtained by vulcanizing a rubber composition having a synthetic rubber derived from petroleum resources of Comparative Example 2 and a conventional anti-aging agent, 300% elongation tensile stress. The crack resistance after 1 year or 2 years was found to be superior to that of Comparative Example 4 using anti-aging agent A. Further, it was found that the discoloration resistance of tires produced using the antioxidants of Examples 6 and 8 was superior to that of Comparative Example 4.
The tire manufactured using the bio-derived anti-aging agent has a browning of the tire surface suppressed for a long period of time, that is, has excellent discoloration resistance. This indicates that the bio-derived anti-aging agent has good compatibility with the rubber component.
Accordingly, as Examples 6 and 8, a vulcanized rubber compounded with a synthetic rubber and an anti-aging agent synthesized from biological resources including plant resources has a vulcanization rate, 300% elongation tensile stress, cracks. It has been found that it is superior to a vulcanized rubber compounded with a comparative conventional anti-aging agent in resistance and discoloration resistance.
Further, the vulcanized rubber of Example 8 in which a part of the raw material is blended with an anti-aging agent C using a petroleum resource-derived material is an example in which the anti-aging agent B in which all the raw materials are bio-derived is blended. It was found to be superior to the vulcanized rubber No. 6 in discoloration resistance.

[0002]
[1] An anti-aging agent synthesized using biological resources including plant resources,
An anti-aging agent having a value of δ13C of the anti-aging agent of −30 ‰ to −26.0 ‰, or −22 ‰ or more.
[2] An anti-aging agent obtained by synthesizing a material obtained from a biological resource including plant resources and a material obtained from a fossil raw material, and the value of δ13C of the anti-aging agent is − Antiaging agent which is 28.5 ‰--26.5 ‰.
[3] The antiaging agent according to [1] or [2], wherein the antiaging agent is synthesized using biomethane obtained from a biological resource including a plant resource as a starting material.
[4] The antiaging agent according to any one of [1] to [3], wherein the antiaging agent is synthesized using biobenzene obtained from a biological resource including a plant resource as a starting material.
[5] The antioxidant is at least one selected from N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,2-dihydroquinoline combination. The antiaging agent according to any one of [1] to [4].
[6] The antiaging agent according to any one of [1] to [5], wherein the antiaging agent is synthesized using acetone obtained from a fossil raw material.
[7] The antiaging agent according to any one of [1] to [6], wherein the antiaging agent is synthesized using methyl isobutyl ketone obtained from a fossil raw material.
[8] Any one of [1] to [7], wherein a biological resource including a plant resource that is a raw material of the anti-aging agent is at least one selected from livestock excrement, sludge, and herbaceous waste. Anti-aging agent as described in 4.
[9] A rubber composition comprising the antiaging agent according to any one of [1] to [8].
[10] A tire comprising the rubber composition according to [9].
[11] Methane from biological resources including plant resources by methane fermentation

[0003]
A process A for obtaining a gas, and a process B for obtaining aniline from the methane gas obtained in the process A using a solid catalyst, and further obtaining N-phenyl-p-phenylenediamine from the aniline obtained in the process B. And the step C of reacting the N-phenyl-p-phenylenediamine with methyl isobutyl ketone obtained from the fossil raw material and the step D of reacting aniline obtained in the step B with acetone obtained from the fossil raw material. The manufacturing method of the antioxidant which has the process of.
[12] The method for producing an antiaging agent according to [11], wherein the value of δ13C of the antiaging agent obtained by the production method described in [11] is −28.5 to −26.5 ‰. .
[13] The method for producing an anti-aging agent according to [11] or [12], wherein the biological resource including the plant resource that is the raw material of the step A is waste biomass.
Effects of the Invention [0006]
ADVANTAGE OF THE INVENTION According to this invention, the anti-aging agent synthesize | combined from the biological origin resources containing a plant resource, the rubber composition with which this anti-aging agent was mix | blended, and the tire using this rubber composition can be provided.
BRIEF DESCRIPTION OF THE DRAWINGS [0007]
[FIG. 1] It is explanatory drawing explaining the method of synthesize | combining an anti-aging agent from the resource derived from organisms containing a plant resource.
BEST MODE FOR CARRYING OUT THE INVENTION [0008]
Hereinafter, the anti-aging agent according to the embodiment of the present invention will be described in detail.
[Anti-aging agent]
The anti-aging agent according to the first embodiment of the present invention is an anti-aging agent synthesized from biological resources including plant resources, and the value of δ13C of the anti-aging agent is −30 ‰ to −26.0 ‰. Or -22 ‰ or more. Here, the value of δ13C of the antiaging agent is measured by a stable isotope ratio measuring device.
[0009]
δ13C represents the ratio of stable isotopes in the substance. δ13C is a ratio of ¹³ C to ¹² C in the target substance, and ¹³ C / ¹² C is compared with the isotope ratio in the standard sample (fossil of Cretaceous belemnite). This is an index indicating how much the deviation is, and this ratio is represented by ‰ (percentage). It means that the ratio of ¹³ C in a substance is so low that the value (negative value) of (delta) ^13C leaves | separates from zero. Light isotopes are more diffusive and more reactive than heavy isotopes. For example, in the case of carbon atoms in atmospheric carbon dioxide incorporated into plants for photosynthesis, ¹² C is better than ¹³ C. It has been found that it is easily fixed in plants. That is, the carbon atoms taken into the plant body have a relatively large amount of ¹² C and a smaller amount of ¹³ C than carbon atoms in the atmosphere. Therefore, the stable isotope ratio (δ13C) of carbon incorporated into the plant body is the stable isotope of carbon present in the atmosphere.

[0006]
Ru-p-phenylenediamine, alkylated diphenylamine, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl-p-phenylenediamine, phenyl-α-naphthylamine, octylated diphenylamine and its derivatives, N, N′-diphenyl-p-phenylenediamine, N, N′-diallyl -P-phenylenediamine, N, N'-di-β-naphthyl-p-phenylenediamine and the like.
Examples of the quinoline antioxidant include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and 6-dodecyl- Examples include 2,2,4-trimethyl-1,2-dihydroquinoline.
The bio-derived anti-aging agents described above may be used alone or in combination of two or more. Among the bio-derived anti-aging agents described above, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,2-dihydroquinoline polymer are selected. At least one is preferred.
The content of the bio-derived anti-aging agent with respect to the total mass of the anti-aging agent is preferably 10 to 100% by mass.
In addition to the bio-derived anti-aging agent described above, the value of δ13C satisfies the above range, the value of Δ14C satisfies −75 ‰ to −225 ‰, or the ^14C decay value per gram per minute is Examples thereof include a phenol-based anti-aging agent, an organic phosphite-based anti-aging agent, a thioether-based anti-aging agent and the like that satisfy 0.1 dpm / gC or more.
[0013]
[Method of synthesizing bio-derived anti-aging agent]
<Synthesis method>
Bio-derived N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl as bio-derived anti-aging agents

[0007]
A method for synthesizing a -1,2-dihydroquinoline polymer will be described with reference to FIG.
FIG. 1 is an explanatory diagram for explaining a method of synthesizing an antiaging agent from a biological resource including a plant resource.
The bio-derived anti-aging agent can be synthesized via benzene using methane obtained from biological resources including plant resources (hereinafter referred to as biomethane) as a starting material.
[0014]
(Biomass → Biomethane: Methane fermentation)
First, biomethane is synthesized from biomass by methane fermentation.
Examples of biological resources that can be used as raw materials for biobenzene include waste biomass such as food waste, food waste, livestock waste, sludge, and vegetation waste. It is known that biogas (methane gas / carbon dioxide = 60/40, including a trace amount of hydrogen sulfide) can be obtained by decomposing these organic substances by microorganisms. By purifying biogas, high-purity methane gas can be obtained.
[0015]
(Biomethane → Biobenzene: Mo / ZSM-5 catalyst)
Next, biobenzene is synthesized from biomethane. A methane conversion rate of 6-12% was reported in a flow-through fixed bed reactor using a 6% Mo / ZSM-5 catalyst at 750 ° C., 3 atm (Patent No. 3755955, Patent No. 3755968, Patent No. 3745885 and Japanese Patent No. 3835765).
[0016]
(Production of bio-derived N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,2-dihydroquinoline polymer)
As shown in FIG. 1, N-phenyl-N′-1,3 is obtained by reacting N-phenyl-p-phenylenediamine obtained from aniline produced from bio-derived benzene with methyl isobutyl ketone. -Dimethylbutyl-p-phenylenediamine can be obtained.
In addition, aniline produced from bio-derived benzene is reacted with acetone.

[0008]
Accordingly, a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline can be obtained.
Here, a part of the raw material used in the process of synthesizing the bio-derived anti-aging agent may be a fossil resource-derived resource or a biological resource including a plant resource. Further, the raw material may be a mixture of a fossil resource-derived raw material and a biological-derived raw material including a plant resource.
From the viewpoint of the discoloration resistance and crack resistance of the rubber composition and tire using the obtained compound, it is preferable to use a fossil resource-derived resource as a part of the raw material.
For example, the above-mentioned methyl isobutyl ketone and acetone can be bio-derived. Hereinafter, a method for producing bio-derived acetone and a method for producing bio-derived methyl isobutyl ketone will be described.
[0017]
<Bio-derived acetone>
As an example of a method for producing bio-derived acetone, there are a method of dry distillation of calcium acetate and an acetone / butanol fermentation method.
In the method of dry distillation of calcium acetate, first, calcium acetate is synthesized from acetic acid obtained by thermal decomposition of biomass or oxidative fermentation of ethanol and calcium carbonate. Acetone is obtained by dry distillation (thermal decomposition) of the obtained calcium acetate.
CaCO ₃ + CH ₃ COOH → Ca (OCOCH ₃ ) ₂ + H ₂ O + CO ₂
Ca (OCOCH ₃ ) ₂ → CaCO ₃ + CH ₃ COCH ₃
Specifically, acetone is obtained from calcium acetate according to the methods disclosed in the following documents 1 and 2.
Reference 1: E.E. G. R. Ardagh, A .; D. Barbour, G.M. E. McClarian, E .; W. McBride, Distillation of Acate of Time, Ind. Eng. Chem. 1924, 16 (11), pp1133-1139.
Reference 2: LF Goodwin, E .; T.A. Sterne, Losses Incurred in the Preparation of Acetone by the Distillation of Acetate of Lime, Industrial & Engineering Chemistry, 1920, 1243 (3), 240-2.

Claims (11)

An anti-aging agent synthesized using biological resources including plant resources,
An anti-aging agent having a value of δ13C of the anti-aging agent of −30 ‰ to −26.0 ‰, or −22 ‰ or more.   2. The antiaging agent according to claim 1, wherein the value of δ13C is −28.5 ‰ to −26.5 ‰. An anti-aging agent synthesized using biological resources including plant resources,
An anti-aging agent having a value of Δ14C of the anti-aging agent of −75 ‰ to −225 ‰. An anti-aging agent synthesized using biological resources including plant resources,
An anti-aging agent wherein the anti-aging agent has a ¹⁴ C decay per gram amount value of 0.1 dpm / g C or more.   The anti-aging agent according to any one of claims 1 to 4, wherein the anti-aging agent is synthesized using biomethane obtained from biological resources including plant resources as a starting material.   The anti-aging agent according to any one of claims 1 to 5, wherein the anti-aging agent is synthesized using biobenzene obtained from a biological resource including a plant resource as a starting material.   The anti-aging agent is at least one selected from N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine and 2,2,4-trimethyl-1,3-dihydroquinoline polymer. Antiaging agent of any one of Claims 1-6.   The anti-aging agent according to any one of claims 1 to 7, wherein the anti-aging agent is synthesized using acetone obtained from a biological resource including a plant resource.   The anti-aging agent according to any one of claims 1 to 8, wherein the anti-aging agent is synthesized using methyl isobutyl ketone obtained from a biological resource including a plant resource.   The rubber composition containing the anti-aging agent of any one of Claims 1-9.   A tire comprising the rubber composition according to claim 10.

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